Non-soap detergent compositions



United States Patent NON -SOAP DETERGENT COMPOSITIONS John Ross, Ramsey,N. J., assignor to Colgate-Palmolive Company, Jersey City, N. 1., acorporation of Delaware No Drawing. Application October 18, 1949, SerialNo. 122,133

2 Claims. (Cl. 252-161) The present invention relates to new syntheticdetergent compositions, and more particularly to compositions of thetype of sulfated and sulfonated aliphatic acylcontaining detergentswherein the acyl radical has about 8 to 22 carbon atoms, having improvedproperties, and to a process for preparingthe same.

Various additives have been incorporated in a wide range ofconcentrations to modify the properties of synthetic detergentcompositions in a desired manner. These additives individually mayeffect one or more of the following properties or mechanisms involved inthe action of the detergent composition including foam volume, foamstability, dispersion, interfacial tension, modification of micellarstructure,-etc. In view of the varied nature of many syntheticdetergents, additives in general exhibit a certain degree of specificityof action.

While the exact relationship, if any, between detergency and foam is notknown, it is preferred that the detergent composition should exhibitexcellent foaming properties, particularly for consumer appeal andcertain home and industrial uses. Accordingly, additives which improvefoam and/or detersive efficiency of a detergent composition are highlydesirable. In general, most testing conditions to determine thesuitability of additives in synthetic detergents have revolved aroundthe use of concentrations of detergent compositions of the order of0.15, 0.2 and 0.25%.

It has now been discovered that the incorporation of minor amounts offatty alcohols of about 10 to about 22, and preferably about 12 to about18 carbon atoms in synthetic water-soluble sulfated and sulfonatedaliphatic acyl-containing detergents having an acyl radical of about8-22 carbon atoms, give improved foam stability and detersive power atcertain selected washing concentrations.

The novel compositions of the present invention containing the selectedfatty alcohols as additives do not show any significant increase indetergency and may even exhibit decreased detergency when employed incertain concentrations, in comparison to the use of these detergentcompositions without the alcohol additives. It has been found, however,that within certain selected washing concentrations a marked andsynergistic increase in detergency results from the use of the alcoholadditives. It may be noted that the total washing power of anycomposition is necessarily the result of the amount of soil removal andsoil suspension or redeposition. Additives in general may increase bothsoil removal and redeposition, or may change one such factor. It hasbeen found, however, that the fatty alcohol additives in thecompositions referred to herein have the desirable properties of bothincreasing soil removal and inhibiting soil redeposition, though theimprovement in the former factor appears to be more pronounced.

1 With respect to the foamingproperties, it has been determined that thesaturated fatty alcohols of about 14 to about 18 carbon atoms exert ahighly beneficial and synergistic action on the foam stability of thecompositions referred to herein, in comparison to the use of otheralcohols as additives. The reason for this specificity of action is notknown at this time.

The synthetic detergent compositions comprised by the invention containas the active ingredient the surface active synthetic sulfated orsulfonated aliphatic acylcontaining compounds wherein the acyl radicalhas about 8-22 carbon atoms. Within the scope of such definition are thehigher fatty acid ethanolamide sulfates; the sulphuric acid esters ofpolyhydric alcohols incompletely esterified with higher fatty acids, e.g. coconut oil monoglyceride monosulfate, tallow diglyceridemonosulfate; the hydroxy sulfonated higher fatty acid esters, e. g.higher fatty acid esters of 2,3 dihydroxy propane sulfonic acid; thehigher fatty acid esters of low molecular weight alkylol sulfonic acids,e. g. oleic acid ester of isethionic acid; and the like. Moreparticularly, it is preferred to use the sulfated and sulfonatedaliphatic carboxylic esters containing at least about 10 carbon atoms,especially those having about twelve to about twenty-six carbon atoms tothe molecule, which may be derived from fatty oils, mono anddi-glycerides, partial fatty acid esters and ethers of polyglycols, etc.

These detergents are commonly used in the form of their water solublesalts. Of these, the alkali metal (e. g. sodium, potassium) and ammoniumsalts are preferred though other salts such as the amine, alkylolamine,alkaline earth metal (e. g. calcium, magnesium) salts may be used ifdesired. Their concentration in the detergent compositions of thepresent invention is generally at least about 10, and preferably atleast about 20% by weight of total solids. Compositions with very highconcentrations of these active ingredients of the order of up to aboutare prepared for specialized uses generally. With built compositions,however, it is preferred to use an active ingredient content of about 20to about 50%.

The fatty alcohols used as additives in the present invention are thoseof about 10 to 22, and preferably of about 12 to 18 carbon atoms. Theseessentially aliphatic alcohols may be primary or secondary; andsaturated or unsaturated in character. It is preferred. however to usethe saturated straight-chain primary alcohols of about 14 to about 18carbon atoms. Examples of suitable alcohols falling within the broadclassification are lauryl, myristyl, cetyl, stearyl, oleyl, palmityl,etc. It is not necessary to use the pure substances themselves as thecommercial mixtures of these substances are also operable and may bepreferred from the viewpoint of economy. Thus, commercial mixtures offatty alcohols containing predominantly the desired fatty alcohols areincluded within the scope of this invention, even though such mixturesmay contain minor amounts of fatty alcohols of different chain length.

The fatty alcohols may be derived either from natural or syntheticsources. Many naturally occurring wax esters are an important source ofhigher aliphatic alco hols. Certain animal oils, chiefly those of marineorigin such as sperm oil, also contain a high proportion of re coverablealcohols occurring as esters. The most plentiful and economic sourcesfor their production, however, are their preparation from fatty acids oraldehydes by reduction, or their recovery from oxidized petroleumstocks, etc., by processes known in the art.

These additives may be incorporated with the active ingredient at anypoint during the manufacturing process at which subsequent operationswill not adversely modify effect on its foaming and detergencyproperties.

the properties 'of the detergent composition. In general, this additionmay be accomplished by adding the alcohols to the active ingredienteither in liquid form, or by mixing those materials which are solidunder normal conditions in comminuted form. The best results are notachieved by mechanically intermixing the comminuted solid components.Avariety of procedures, which have proved to be convenient, economical,and productive of the best results arei 1. The addition of the fattyalcohols in 'a molten state to a hot aqueous slurry of the activeingredient of about 40 to 50% concentration with vigorous stirring toform a smooth, uniform and homogeneous paste.

2. The fatty alcohols may be dissolved in a suitable solvent, e. g.ethanol, and added to a slurry of the active ingredient.

3. A cream emulsion of the fatty alcohols in water with a minorproportion of the active ingredient may be prepared and incorporatedinto the slurry of active ingredient in the manner set forth above.

Thereafter, these compositions may be made up in the form of solutions,pastes, or as dry or partially hydrated solid products, preferably in afinely divided condition.

The amount of these added long chain alcohols is generally minor inproportion to the weight of the total detergent composition andsufficient to produce a marked Generally, the amount of each additivevaries within rather definite proportions of the order of about i toabout by weight since is has beenldeterrnined that within these somewhatcritical limits the desirable effects appear to be attained to a maximumdegree. With built compositions, it is preferred to useabouta 1 to about5% concentration of alcohols.

With respect to detergency, it has been found that the fatty alcoholadditives perform the dual function of increasing the soil removal powerand of inhibiting the soil redeposition factor of the detergentcompositions referred to herein. The unitary effect on detergencyresulting from a concurrent activationof one factor and repression ofanother is of a synergistic character, since the fatty alcohols per sehaveno deterging power. One of the most significant aspects of thisimprovement however is the fact that it may be noted only when used in aparticular manner. The compositions of the present invention containingthe free alcohols in general do not show any significant increase indetergency and even may exhibit decreased detergency when employed inwashing concentrations of the order of 0.150.25%. It has been 'found,however, that under washing concentrations such as 0.40.75% a markedincrease in detergency results from the use of these alcohols asadditives.

These various results are evident from a consideration of the followingdata and examples described hereinafter which are merely illustrative ofthe present invention and it will be understood that the invention isnot limited thereto.

Tables I and 11 indicate the changes in washing power at various bathconcentrations in soft and hard water of a detergent compositioncontaining 23% sodium salt of coconut oil monoglyceride sulfate as theactive ingredient, 2% of a 90:10 mixture of cetyl and stearyl alcohol,50% tetras'odiu'mpyrophosphate, 3% sodium silicate and 22% sodiumsulfate.

The washing procedureinvolves the uniform soiling, washing at 110 RiZ"F. and drying of a large number of cotton swatches. The whiteness of thevarious test swatches are measuredby a Hunter reflectometer. The unitsof soil removed may be calculated by subtracting the averagereflectivity of the unwashed control samples from the washed swatches.The effect on redeposi tion of soil in the fabric is determined byplacing unsoiled samples in the detergent bath together with the soiledsamples and measuring the brightness after washing. The numbers in thetables represent the change in units of soil removed and redepositedwith the use of the above detergent composition with and without thefatty alcohol additives. A value indicates an increase in soil removaland redeposition; a value indicates a decrease in soil removal andlesser redeposition of soil.

Table l.--Soft water solutions Soil Re- S011 Redep- PercentConcentration moval 051mm Table II.--Hard water (300) p. p. m.)solutions It may be noted from the above data that no significantimprovement in total washing power is attained either in hard or softwater using concentrations of 0.15 and 0.25%. .In fact, at lowconcentrations in hard water decreased detergency may result from theuse of the alcohol additives. At higher concentrations however, a markedand synergistic increase in detergency results from the use of the fattyalcohol additives, particularly due to improved soil removal power. Itis not completely understood why these additives in the relationship setforth should exhibit this unique specificity of action.

Though the sulfonated and sulfated detergent compositions referred toherein containing the alcohol additives may be used as a relatively puremixture of these components, it is common however to employ variousadjuvant materials in synthetic detergent compositions. These buildersor additives may be inorganic or organic in structure, and may beadmixed with the active ingredient in any suitable manner. Such adjuvantmaterials may include any of the substances employed by neutralize orremove the effectiveness of the fatty alcohols. It has been found thatthese added materials may vary greatly both in structure and inconcentration without impairing the improved results of the compositionsreferred to herein.

Thus, such convenient inorganic builders or additives as the silicates,various alkali metal phosphates (e. g. hexametaphosphate,tetrapyrophosphate), the alkali metal sulfates, carbonates, etc., may beemployed in these compositions. Organic materials such as carboxymethyhcellulose, esters (e. g. ethylene glycol monostearate, methylpalmitate), and the like may also be used under suitable conditions. 7 Y

Of the indicated vast variety of known builders and additives which maybe employed in detergent 'cornp'ositions, it has been found that thewater soluble polyphosphates in conjunction with the mixed organicadditives have remarkable effects on the sulphonated and sulphatedacy'l-containing detergent compositions. 'Thepolyphos phates arepreferably the water soluble inorganic tri-polyphosphates of theformula:

M representing an alkali metal or ammonium group. vThe actions of thetri-polyphosphate and the fatty 5. alcohol additives in these detergentcompositions are not only not antagonistic, but mutually contribute to abalanced detergency system such that a unitary result of vastly improveddetergency is achieved thereby.

As previously indicated, the effect of the alcohol is primarily one ofactivation of the soil removal power of the detergent compositionsreferred to herein with a more moderate inhibition of the amount ofsoilredeposition. It has been determined however, that thetri-polyphosphates appear to exert beneficial results in an oppositedirection in these detergency systems. The tri-polyphosphates exhibittheir greatest effect on soil suspension or prevention of soilredeposition, and only to a minor extent on the soil removal factor.Since the total washing efficiency is due to a combination of both soilremoval and soil suspension, it is apparent that the mixed additives ofthe organic fatty alcohols and the inorganic water solubletri-polyphosphates mutually contribute to produce a somewhat balancedelfect since both the two factors of improved soil removal and lessenedsoil redeposition are activated concurrently to a significant degree.

These unexpected results are not achieved to the same degree when otherphosphate compounds, such as tetrasodiumpyrophosphate (Na4P2O7) ortri-sodiumphosphate (NasPOr) are substituted for the tri-polyphosphates.It is not known at this time why the indicated washing mixtures with thetripolyphosphate should yield a markedly superior cleaning performancecompared to mixtures with other phosphates in the detergent systemsreferred to herein.

These tri-polyphosphates may be used in any desired proportion. To someextent the degree of improvement appears to be proportional to itscontent in the composition. In general, the greater the percentage oftri-polyphosphate, the better the result where the active ingredient hasbeen maintained constant. It has been found that best results areattainable when the ratio of tri-polyphosphate to the active ingredientis at least about 1:1. For maximum efliciency of these compositions, theactive ingredient should be present in an amount at least about byweight of the total composition. A proportion of active ingredient fromabout 20% to up to about 50% with a similar proportion of thetri-polyphosphates and a minor amount of the higher fatty alcoholsproduces sufficient deterging properties for even heavily-soiledlaundry; and such compositions are economical to prepare and convenientfor use in the home or commercially.

The tri-polyphosphates may be incorporated with the active ingredient inany suitable manner. It is possible to mechanically intermix theseconstituents in the form of small solid particles. It is preferred,however, to apply the techniques set forth above for the introduction ofthe higher alcohols. Thus the tri-polyphosphates may be added to aslurry of the active ingredients before, during or after incorporationof the alcohols. The resulting mixtures may be dried in any convenientmanner e. g. roll or spray dried. Excessively high temperatures duringdrying should be avoided however to prevent substantial decomposition ofthe polyphqsphates.

It is a significant feature of this invention that the long chainsaturated primary alcohols of at least about 14 carbon atoms exert abeneficial effect on the foaming properties of the synthetic non-soapaliphatic acyl-containing sulfated and sulfonated detergents wherein theacyl group has 8 to 22 carbon atoms. The desirable effect of these fattyalcohols on the foam of such detergents as the fatty acid monoglyceridesulfates, fatty acid ethanolamide sulfates, etc., is unique and inmarked contrast to the general adverse effect on foam produced by thesealcohols on other sulfonated and sulfated detergents.

These fatty acyl-containing detergent compositions containing the fattyalcohol additives are characterized by increased stability of the foamproduced in washing operations in comparison to the foam effectsproduced by 6 these compositions without the fatty alcohol additives.The fact that these alcohol adducts in the particular relationship setforth produce foams and suds which are more stable, do not readily breakdown by evaporation, have in general longer drainage time and containmore liquid, are significant and desirable properties for a detergentcomposition.

Moreover, it has been found that in general, the alcohol adducts inthese compositions tend to increase the tolerance of these detergentcompositions in the assimilation or holding in suspension of a maximumamount of dirt, grease, etc., with less foam loss than is found withoutthe use of these additives.

The effects on the foaming characteristics can be studied quantitativelyfor a given composition by means of a foam consistency test. Briefly,this test consists of the formation of a foam by standardized agitationof 500 cc. of a detergent at F. in a two quart unsilvered Dewar flask.The foam formed after a 10 minute agitation period is then measured witha consistometer after standing for 5, 10 and 15 minutes. The readingsare an indication of the foam consistency or bodying effect. It has beenarbitrarily determined using a standard consistometer that a value belowabout 275 units represents relatively low viscosity, a value of 275-350units intermediate consistency, and above 350 units is high consistency.

This consistometer is a means for measuring the mini mum torquenecessary for rotation of a paddle of any standard size through a foam.This device applies the torque by means of a coil spring which has itsinner end attached to a paddle shaft and the outer end attached to acircular plate which can be rotated. The degrees through which thespring may be twisted before the paddle starts to move in the foam maybe readily determined. An indicator needle is attached to the top of thepaddle shaft and a circular scale divided into 360 is set on the platewhich holds the outer end of the spring. The paddle shaft is held inplace by a pair of ball bearing races in such a way that it can turnfreely.

A foam consistency test is conducted in distilled and in hard waterusing a detergent composition comprising essentially 30.9% coconut oilmonoglyceride sulfate salts, 7.5% sodium phosphates, and the remaindersodium sulfate with and without alcohol additives. The results using0.25% concentration of the detergent composition are set forth in thetables below. The values given therein represent the averages of thethree readings at 5, 10 and 15 minute intervals.

The data in the table above indicate the remarkable effectiveness of thesaturated straight-chain primary alcohols of 14 to 18 carbon atoms asfoam stabilizers on such detergent compositions. It may be notedthatdodecanol containing 12 carbon atoms is ineffective to increase thefoam consistency. Tetradecanol and octadecanol give intermediate to highfoam consistency. The hexadecanol appears to represent an optimum inregard to chain length. It is also evident moreover, that combinationsof fatty alcohols consisting essentially of C14 to C13 are effective inimproving the foam stability of the detergent composition.

57 The. improved. results are also observable 1 in .hard wateras-disfclosedf'in'TableIIbelow:

ksynthetic'mixtures ;of fatty,alcohols corresponding to fatty acidcompetitions or the indicated fats and oils.

.It iseVident-that the:fatty ,alcohols containingessentially CIA-.Cl-Balcohols-are highly effective to improve :the .foam .consistency in.hard water. .It vmay .be noted that synthetic mixtures of these:alcohols corresponding to ..the.fatty acid scompositionof various fats:an'd oils which predominate .in fatty acids of :14 to 18 carbon atomsarealso highly effective in the relationship set forth. lnnumber 7 of.Table -II, -a 2:1 mix of hydrogenated tallow and coconut .oilalcoholsisused to determineif thepresence .ofzminor amountsof coconut oil alcoholspredominating ,inxcl2 :alcohols would neutralize the effectiveness.ofthehigher homologues. ltmay be noted that snchajmixture maintainsrelativelyhigh consistency inhard water,.thereby indicating thatminor'but significant .amounts.of alcohols of less-than 14 carbonatoms-may baa-incorporated in the fatty alcohol mixtures used to .giveimproved. results.

The beneficial results derived .using the-organic aciditives referred toherein are: exhibited with varying concentrations -of active ingredientsas set forth in Table III.

TABLEIII Composition Fqam Consistency ALL, 4Cetyl alcohol, SG'NaiSOr 380A; I., 4 Cetylalcohol; 8I-Na' SO4 440 A. L, 4. Cetyl alcohol, 76 NazSOi.420 40 A 1., 4 Cetyl alcohol, 56 NfiZSO-l 4 10 60 A L, 4 Cctyl alcohol,36 NaQSO. 430 80 A. 1., 4 Cetyl alcohol, 16 NazSOe 430 TABLE IVConsistency .Additive Percent in Distilled Water lfiflNone 220 :2. Lorol1 '5 .225 3. Tetradecanol 2 130 "4. HexadecanoL. 2 410 :5. 'OctadeeanoL.2 370 6. Oleylalcohbl. 5 220 L 1 Fatty'alcohol'mixturdderivedfromcoconut' oil.

Tt'is evidenfifrom'the datain'the table ,iaoove fthatithe saturated-fattyalcohols. of .14 .to 18-. carbon atoms aresuperior'foamstabilizing agents.

EXAMPLE .I

The .foam :consistency test is repeated on a detergent compositioncomprising 40% of the condensateofcoconut-oil fatty acids withisethionicacid as .the active ingredient-and 2% lauryl alcoholas-t'ne.organicadditive. .This detergent composition exhibits a foamconsistency05230. -With the;substitution.of..2%cetyl alcohol as theorganic-additive, however, thereis obtained a foam consistency valueof360.

"EXAMPLE '11 Using .a'0.25% .concentration in distilled water of adetergent-composition comprising 40% of the condensate dfcoconut oilfatty acids with methyl taurine .and "60% sodium sulfate, there isobtained a foam consistency value of .220. "With .the addition of 5%'lauryl alcohol a consistency value o'f2'20is.also obtained. Using\2.%.

cetyl alcohol as .the organic additive, improved foam stability ,isobtainedsince the detergent composition. has a consistency value.o'f1390.

EXAMPLE I II Usingan 0.25% concentration in distilled water of adetergent composition comprising 30% magnesium coconutoil monoglyceride.monosuifate as the active ingredient, there'is obtained a foamconsistency value of .230. With the addition of 2% 'cetyl alcohol,a'foam consistency valueof 410 is obtained thereby indicating improvedioamstabilityidueto.thepresence of the alcohol additive.

.Certain, general conclusions. are. apparent. from. the. many testswhich'have been conducted to determine the effectivenessof the longchain fatty alcohols inthe relationship set forth. The mostappropriatefattyalcohol and its .mostefiective concentrationfor each particularsulphonate d or sulphated carbonyl-containing detergent composition may.suitablybedetermined by routine controls. lneachcase the intended use(e. g. hard or soft water, hair shampoos-or machine Washingcompositions, etc.) and the proper washing conditions should be takeninto consideration in order to derive the maximum-beneiicial effects.

Theterm consisting essentially of as used in the definition of theingredientspresent in'the composition claiinedis intended to. excludethepresence of. significant amounts ofother syntheticdetergents andOfOthBIimaterialsin such amounts asto interfere substantially with theproperties and characteristics possessed. by the composition setforthzbut to permit the .;presence of other materials inssuch amounts asnot. substantially to affect said properties and characteristicsadversely.

Although the present invention has been described with reference toparticular embodiments'andtexamples,

it willbeapparent to those skilled inthe art that variations andmodifications of this invention can be made and that equivalents can'besubstituted therefor Without departing from the principlesand truespirit-of the invention.

Having described theinvention, what is desired to be secured by LettersPatentis:

1. A detergent composition consisting essentially of a water-solublehigher fatty acid monoglyceride monosulfate detergent having about"8-22carbons in the fatty acyl group, and'in minorproportion thereto and fromabout lto-a'bout 10% by-weight of a primary'saturated monoh-ydric'fattyalcohol of about 14 to 18 carbon atoms.

2. A detergent composition consisting "essentially 0f a :water-solublehigher fatty acid monoglycer-ide monosulfateidetergent having aboutB-ZZcarbons in the fatty :aryl .group, .and :in :.minor zpro'portion'thereto and from about Tl rtoieabout :by weight:ofcetylraicohol.

7 (References on. following .page) References Cited in the file of thispatent UNITED STATES PATENTS 2,166,314 Martin July 18, 1939 2,366,027Henke Dec. 26, 1944 5 2,396,278 Lind Mar. 12, 1946 10 Strain Nov. 1,1949 Miskel Aug. 15, 1950 Preston Oct. 24, 1950 FOREIGN PATENTS GreatBritain Apr. 19, 1937

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER-SOLUBLEHIGHER FATTY ACID MONOGLYCERIDE MONOSULFATE DETERGENT HAVING ABOUT 8-22CARBONS IN THE FATTY ACYL GROUP, AND IN MINOR PROPORTION THERETO ANDFROM ABOUT 1 TO ABOUT 10% BY WEIGHT OF A PRIMARY SATURATED MONOHYDRICFATTY ALCOHOL OF ABOUT 14 TO 18 CARBON ATOMS.